Process for recovering alkyl phenols from petroleum oils



w. J. HUND ET Al. FROCESS vFOR RECDVERING ALKYL I HENOLS ROM PETROLEUM OILS `lune 4, 1940.

Filed May 25, 1937 Patented June 4, 1940 PA'rENr ori-ICE PROCESS Foa REcovEalNG Amun. 'i PnENoLs FROM PE'raoLElJMVoms ,wal-ters. numana samuel Benson Thom. f Oakland, and YDaniel B. Luten, Jr., Berkeley,

` y' Calif., assignorsy to Shell Development Com- 1 Y. pany, San Francisco, Calif., a corporation of Delaware Application May25, 1937, Serial No. 144,658

8 Claims. K (Cl. 26o-627) Thlsfinvention relates to a v method for economically recoveringv the minute quantities of alkyl phenols contained inpetroleum oils, especlally in cracked distillates, and more particularly deals with a method for recovering such alkyl phenols in a'commercially pure state by simple and inexpensive means." I

While in terms of absolute quantities petroleum oils constitute an enormous potential source 10 of alkyl phenols, the concentration of the latter in petroleum oils is so low and yields have been so poor as to make their extraction commercially unattractive. Furthermore, alkyl phenols recovered from petroleum oils byeiicient extraction are usually contaminated with many different impurities, which have necessitated extensive and costly purification processes in order to produce commercially useful products comparable in quality with those obtained from coal tars. It is the purpose of this invention to recover substantially completely the small amounts of 4 alkyl phenols contained in petroleum oils and to purify them economically. and to a degree suflicient-to meet current commercial standards. Alkyl phenols are used primarily -in the manufacture of resins of thetype Lof formaldehydephenol resins, as flotation and frothing agents in the flotation of ores, gum inhibitors in gasoline and oxidation inhibitorsin general, in the synthesis of cresyl phosphates which are useful as solvents and extreme pressure dopes for lubricants, etc. Alkyl phenols used in the manufacture of resins require an especially high degree of purity, and the expression commercially v3&5 pure as herein used signifies a degree of purity required by the above uses.

Our process consists essentially of the following four main steps:

(l) Extracting a petroleumoil containing alkyl 40 phenols, while in the liquid state, with an aqueous alkali metal hydroxide solution of an original concentration of i-50% under conditions to form two layers and separating the layers;

(2) Subjecting the aqueous layer to a pro- 46 longed steaming with substantially saturated steam to drive off certain impurities and to precipitate a sludge which is separated, and continuing to steam until no further sludge precipitates; v 50 (3) Carbonating the steamed clear liquid aqueous layer with carbon dioxide to liberate alkyl phenols, thereby forming two layers,'and separating the layers;

4) Rapidly distilllng the liberated alkyl phenols under vacuum.

If desired the distilled alkyl phenols may be further purified by oxidation, preferably with air at a temperature between about l40l50` C. followed by redistillation, and the redistilled product may further vbeblown at about room temperature to remove possible foul odors.

The difficulties encountered when attempting satisfactorily to recover "and refine alkyl phenols from petroleum oils are tol some extent 'reflected in the patent literature. In the past various rather involved methods have been suggested for the puriiication vo1' alkyl phenols derived from petroleum oils. Thus, Blair in U. S. Patent 1,933,410 describes a ,method comprising acidiying an alkaline extract from a cracked petro-y leum distillate` to liberate organic acidic sub` stances, and separating and distilling the same to produce a fraction boiling between 180 to 275 C. 'IEhis fraction is reduced to convert disulfides to mercaptans. The reduced acids are 20.

fractionally distilled to produce several fractions, the several fractions are air blown to recouvert mercaptans to disulfldes, and the latter are separated from the` fractions by distillation.

Drennan, in U. S, Patent 2,048,784, suggests 25 extracting petroleum oil containing alkyl phenols with'aqueous alkali metal hydroxide of Ztl-25% concentration,A further extracting the alkaline phenolate solution so obtained with an organic liquid such as butyl or amyl alcohol, transferring 30 the phenolate from the alcohol into water, removing the excess water by distillation, and steaming the residue. y

Merrill, in U. S. Patent 2,000,244, proposes to extract acidic components from petroleum with 35 aqueous alkali metal hydroxide and acidifying the resulting solution to liberate the acidic components. To the liberated oily layer sodium carbonate is added to neutralize naphthenic acids but notyphenols. After further adding some 40 Edeleanu extract of kerosene or the like to the neutralized layer, the latter is distilled with steam. Water, neutral oil and phenols are taken overhead and condensed. The condensate is again extracted with aqueous alkali metal hydroxide and the resulting aqueous solution is acidiiied, liberated alkyl phenols are separated and are further distilled over sodium carbonate.

.The above described as well asy other known methods have one or several disadvantages. Either they entail poor recovery of alkyl phenols due to incomplete extraction or high treating losses, or they yield products incapable of meeting the commercial standards, or they consume an excessive amount of chemicals due, for inlamounts thereof. Since phenol,

stance, to double caustic extraction and acidification. In no instance has it been vpossible to recover substantially all alkyl phenols from petroleum oils in a commercially pure state by a method involving a consumption of chemicals not materially greater than required in our process hereinafter described in detail.

Diierent petroleum fractions contain Widely different amounts of alkyl phenols. Most straight run oils contain very little, if any. `While cracked oils often contain relatively large the lowest boil-l ing member of the group of hydroxy aromatic compounds, boils at about 180 C., it is reasonable to expect that distillates boiling below about 175 C. contain no phenols or alkylv phenols. Cracked distillate fractions boiling between about 175-300 C. usually contain appreciable quantities, and concentration peaks' normally appear in the fractions boiling between about 180-230 C. In order to reduce the volume of petroleum oil to be extracted, it is therefore desirable fractionally to distill the petroleum oil to separate a fraction comprising an alkyl Vphenol concentrate which phenols. Y

'I'he step of extracting the petroleum `oil consists essentially of treating the liquid oil with an amount of an solution, preferably sodium or potassium hydroxide, of an original concentration of 3 5-50%, which amount contains a quantity of free hydroxide only slightly in excess of that. required to convert all of the alkyl phenols contained in the oil to alkali metal alkyl phenolates. It is known that when alkyl phenols are added to caustic of about 35-50% concentration a precipitation of phenolates takes place, and upon further addition of a certain minimum critical amount of alkyl phenols, which amount is less' than that required to consume all of the free alkali metal hydroxide, the precipitated phenolates are redissolved inthe aqueous phase. Thus by adding to an alkali metal hydroxide solution of the above strength the minimum critical amount of alkyl phenols required to form a single aqueous phase of phenolates, a solution is obtained which contains besides the phenolates considerable quantities of free alkali metal hydroxide. This critical amount varies considerably with the concentration of the hydroxide and the type of alkyl phenols added. For instance, when using a mixture of alkyl phenols of an average molecular weight of xylenols, the critical amount required to produce a single phase would be asfollows for aqueous sodium hydroxide solutions of various concentrations Critical amount of alkyl phenols percent by weight oi solution Original concentration ot N aOH in caustic olution sans The resulting phenolate solution containing free alkali metal hydroxide is the most effective extractant for alkyl phenols from hydrocarbon oils, if contacted with the oil in the proper proportion. The amount of alkaline alkyl phenolate solution used to treat a given amount of oil containing alkyl phenols should be such that the amount of alkyl phenols in the oil is suiiicient to convert a portion only of the free alkali hydroxide contains the Ybulk of the desired *petroleum oil. is accomplished, the alkyl phenols aqueous alkali metal hydroxide to alkali phenolates,` and the enriched phenolate solution thus produced should preferably contain a. mol ratio of alkyl phenols to alkali metal between the limits of .80 and .98.

In its most eflicient form the extraction is carried out as follows: An alkaline alkyl phenolate solution containing at least the critical amount of alkyl phenols is continuously circulated. At some point of the circuit it is contacted with an amount of oil containing alkyl phenols, so that a substantial portion of the free alkali hydroxide is converted to phenolates. 'I'he oil and the aqueous phenolate solutions are then separated, the oil being substantially free from alkyl phenols after this extraction. A portion of the phenolate solution is then withdrawn from circulation to be treated as will be described hereinafter. 'I'he remainder of the alkyl phenolate solution is mixed with an amount of fresh caustic of 35-50% concentration suiicient to replace the amount of alkali metal withdrawn before, mixture containing free alkali is again contacted with fresh oil-as described above.

While by this method of extraction substantially complete removal of alkyl phenols from so.- extracted are highly contaminated with impurities. Besides alkyl phenols, other substances are dissolved in the aqueous phenolate solution, notably. naphthenic and other carboxylic acids,

neutral hydrocarbons, sulfur compounds, nitrogen bases, resinous bodies, etc., and in addition the aqueous solution may contain varying amounts of-emulsifled heavy tarry material, part of which may settle out upon prolonged standing. Alkyl phenols liberated from the untreated phenolate solution byacidiiication may contain 10 o'r more per cent of neutral-oil, sulfur in excess of 1%.-and nitrogen bases as high as 6 or 8%.

The phenolate solution lcontaining neutral, basic and sulfurous impurities is now subjected to a prolonged steaming preferably at substantially normal pressures and with substantiallysaturated steam. 'I'he use vof highly superheated steam or the heating of the `phenolate solution substantially above 100 C. isdisadvantageous because it leads to excessive losses of lalkyl phenols by vaporization and by way of undesirable condensation and/or decomposition reactions of the phenols themselves.

This steaming in combination with the described method of extracting the alkyl phenols from the petroleum oil is the most essential part Unless it is carried far enough 1t is almost impossible to obtain by any subsequent treatment, or combination of simple treatments. except by double use of droxide extraction and acidification as forinstance described by Merrill in U. S. Patent 2,000,244, alkyl phenols of suicient stability and purity to meet even the most liberal commercial requirements.

During the early stages of the steaming period, neutral oils, nitrogen bases, sulfur compoundsand a small portion, amounting to less than 20%, of the alkyl phenols ofrelatively low acdities are vaporized and removed overhead. Steaming, however, must be continued for some time after removal of the volatilizable compounds has been substantially completed. This point is recognized when the exhaust steam, upon condensation, no longer turns turbid. While steaming proceeds, sludge is being formed and precipitated, and when the phenolate solution is allowed to rest, two separate layers form, an aqueous layer and a and the resulting alkali metal hy- 'v 2,908,217 layer. Upon continued steaming tive impurities, it also appears that vthere are heavier sludge the amount of sludge formed eventually reaches a maximum, so that when the sludge is separated and the desludged aqueous layer is further steamed. no additional sludge is formed. The timeofsteamingrequiredtoreachthispoint of maximum sludge formation normally varies between about 4 and 18A hours, alkyl phenolates derived from relatively low-boiling distillates normally requiring shorter time for complete steaming than alkyl phenolates obtained from heavier oils.

It is absolutely essential that steaming be carried out to the maximum point of sludge formatron. While the reactions responsible for the formation of sludge are not quite understood, it appears that its production is due to a combination of removing neutral oils which act as dispersers for actual sludge. i. e., sludge which is present from the beginning, and condensation reactions which take place during the steaming after removal of neutral oils and lead to the formation of additional sludge, for convenience called herein potential sludge. Apparently nitrogen bases take active part in these condensation reactions forming high boiling compounds, and although a considerable portion of the nitrogenous condensation products may remain in the alkaline solution after steaming they later form part of the tarry residue produced in the subsequent vacuum distillation of the liberated alkyl phenols. It appears that considerable time is required to condense the nitrogen bases, and if steaming is too short,y condensation remains incomplete and the unreacted portion thereof will go overhead in the subsequent vacuum distillation jointly with the alkyl phenols. Since nitrogen bes, together with sulfur compounds are the most harmful and obnoxious impurities in commercial alkyl phenols, it is readily seen how important itis to conduct the steaming to the point of maximum sludge formation.

We are aware that alkyl phenols have been produced by extracting coal tars with aqueous caustic, blowing the extract with steam, liberating the phenols an'd distilling and blowing same with air. However, in contrast to the above, phenolate solutions obtained from coal tar distillates with alkali metal hydroxide solutions of customary concentrations, which are generally; much lower than those hereinbefore described, do not produce sludge upon steaming, perhaps because phenolatesolutions obtained with relatively weak alkali hydroxide solutions are comparatively little contaminated with impurities and also because coal tar phenols, having been in contact with ammonia at elevated temperatures y in the course oftheir formation have already undergone a preliminary purification process.-A

But, whereas extraction of phenols from coal tar distillates with relatively weakalkali hydrox. ide solutions is commercially ,practical` becausey theconcentration of phenols-in these dlstillatesv may be of the order of "Ito 35%, (see U. S. Patent 1,991,979) the concentration 'of alkyl phenols in petroleum oils is usually below .5% and. more oitenabout .1% or below. Obviously more eilective meansoffextrai'stionl must `be applied to petroleum oils to coal tar distillata, and thev greater eiiiciency of extraction is vat lleast partly responsible for the greaterdiillculties experienced in the subsequent reiining of the alkyl phenols, which are normally associated .with petroleum beingextracted as well. i

Aside from the relative amounts of the respecconsiderable diilerences regarding their nature. As pointed out before, in petroleum alkyl phenols a class of little known nitrogen bases constitutes the most harmful impurities, which nitrogen compounds seem to be almost 'completely absent from coal tar phenols. For this reason the extent of' the steaming just suilicient to remove neutral oils has proven adequate in the purification of coal tar phenols, but in the case of puriilcation of petroleum phenols has met with failure; and before our discovery that steaming must be prolonged to give time for the'condensation reactions described above it wasv impossible to obtain commercially pure alkyl phenols in the simple manner proposed by us.

When the steaming has progressed so thatupon further steaming no additional sludge is formed, the precipitated sludge is separated from the phenolate solution. Usually the desludged solution contains emulsiiled-organic matter other than sludge, which refuses to separate at this point. In such a case diluting the phenolate solution with atleast an equal volume of water will readily break the emulsion. We have found it very lconvenient as a rule to dilute the solution to about 10%. If this does not produce a complete break of the emulsion, resort may be had to centrifugation or filtration through a suitable medium which is preferentially wetted by the organic matter.

The phenolate solution is now perfectly. clear y and of much lighter color than before steaming, since neutral oils capable of dissolving sludge have been removed substantially quantitatively as well as most Asludge-forming compoundsand a p ortion of thel sulfur compounds. This clear phenolate solution is now carbonated by introducing into it carbondioxide or a gas containing carbon dioxide such as flue gas, or lime kiln gas, etc.,

in an amount so that preferably the resulting aqueous solution contains about an equi-molar mixture of carbonate andy bicarbonate. Since4 phenols are acids weaker than carbon dioxide,

they are liberated while the stronger carboxylic acids as wellas hydrogen sulde, if present, remain in` the aqueous solution as alkali metal salts. Together with the alkyl phenols, organic hydrosuliides such as thio phenols .and mercaptans .not removed vby steaming, are liberated IIhe liberated alkyl phenols form a separate layer and are removed from the resulting. aqueous carbonate solution in which the Acarboxylic acids are ret9.ined. The alkyl phenols may.bewater1washed,

such a wash usually lowering the :sulfur content by about l. 2 to ,3%. Iyf desired, the carboxylic acids be liberated and recsweredvfrom the carbonated' solution,y for instance by treating vsame with a relatively ystrong y,acid,such as sulsulfurous, hydrochloric,v phosphoric acid,

- 'Ihe separated alkyl phenols which r,usually containafrelatively small'amountoi sulfur compounds and more or less'of darkcoloredreslnous or tarrymatter, are now subjected tota quick distillation, preferablya ilash distlllatlon'under a reduced pressure, e.v g., vbelovvabout 25 mm. mercury.. Since'the resinous' or tarry'compounds associated with the 'crude alkyl lphenols are thermallyunstable Aandl cracky'ery'l readily, thereby stage of the process by precision fractionation is 75 not practical, excepting the removal of residual tarry compounds and the like, which can be separate in a rapid flash distillation, and the production of fractions of different boiling ranges. If the steaming of the phenolate solution has been carried out to the point of complete sludge separation as hereinbefore described, close fractional distillation for the purpose of purification other than removal of tar or to obtain sharp cuts is quite unnecessary.

The disiillates resulting from this treatment are mixtures of alkyl phenols of relatively light colors and fair color stabilities, substantially free from neutral and basic organic compounds, and having moderate sulfur contents. If products of still higher color stability and lower sulfur content are required, the distilled alkyl phenols may be subjected to an oxidizing treatment under conditions to oxidize organic hydrosulfldes such as thio phenols and rnercaptans to disulldes or sulfonic acids, without substantially oxidizing the phenols. This can, for instance, be accomplished by blowing with an excess air at a temperature between about 140-150 C., if desired in the presence of an oxidizing catalyst which is not floated by alkyl phenols such as a sulfide of Ni, Co, Pb, Cu, etc. During this oxidation unstable phenols are also converted to high boiling tarry substances, the latter being readily removable by a subsequent redistillation. Distillates so obtained occasionally have a foul odor which, however, can easily be removed by blowing with air at; normal room temperature.

Referring now to the attached drawing in which a liow diagram of a preferred form of our process is shown, tank I contains a petroleum oil containing alkyl phenols, such as cracked distillate boiling, for instance, between 180-230 C. This distillate is pumped by pump 2 in line 3 to mixer 4. An' aqueous alkali metal alkyl phenolate solution containing free alkali metal hydroxide is introduced by pump 6 in line 5, into mixer 4 where it is mixed with the distillate. 'I'he proportions of distillate and alkyl phenolate solution are such that the amount of alkyl phenols in the distillate is but slightly less than that which would be required to convert all of the free alkali metal hydroxide in the phenolate solution to alkali metal phenolate. The resulting mixture then passes through line 'I to settler 8 in which treated distillate substantially free from alkyl phenols rises to the top and is withdrawn through line 9. Aqueous alkyl phenolate solution is conveyed through bottom line I0 and is split into two portions, one of which is recirculated through lines II and 5 by pump' 6 to mixer 4 and the other of which is conducted through line I2 to tank I3. An amount of fresh alkali metal hydroxide of 35-50% concentration having an alkali metal content equal to that of the portion withdrawn to tank I3 is injected into line 5 from tank I4 through line I5, or from line 10, as will be described later. The amounts of phenolate withdrawn from the circulating stream and of fresh alkali metal hydroxide added thereto are preferably such that the concentration of alkyl phenols in the phenolate solution never drops to or below the critical point at which phenolates are precipitated from the solution.

The raw phenolate solution in tank I3 is transferred by pump I6 in line I1 to steaming tower I8 equipped with heating coil I8 near its bottom. In tower I8 the phenolate solution is steamed to remove volatilizable impurities and to precipitate sludge or tar, the steaming being continued for a sumcient time so that upon further steaming no additional sludge is precipitated. Steam is introduced through line I9, and exhaust steam containing vapors of hydrocarbons and other impurities pass through' vapor line 28 and are condensed in condenser 2l. The condensate is separated in settler 22, waste water being withdrawn through line 23 and waste oil through line 24.

When the steaming in tower I8 has been substantially completed in the manner hereinbefore described, the steamed solution is allowed to settle. The heavy precipitated sludge is drawn oil through sludge line 25 and the steamed phenolate solution is transferred by pump 2l in line 26 to settler 28. An amount of water sumcient to permit easy settling of remaining entrained insoluble inorganic matter is injected through line 29 into the phenolate solution passing through line 26. Entrained matter rises to the top of settler 28 and is discarded through line 38.

Settling in settler 28 is continued until the phenolate solution is perfectly clear. The clear solution is then conveyed by pump 3| in line 32 to the top of carbonating tower 33, whence it runs downward over baiiies, bubble plates or other contact means in the tower in countercurrent to carbon dioxide or gas containing carbon dioxide, which is introduced through line 34. Carbon dioxide is absorbed and alkyl phenolates are liberated. Non-absorbed gas leaves the tower 33 through vent line 35 and carbonized aqueous solution passes through bottom line 35 to settler 3l. Liberated alkyl phenols are allowed to rise to the top, and are then conveyed by pump 38 through heater 39 to vacuum tower 40, to be flash distilled and, if desired, fractionated. Several alkyl phenol fractions may be withdrawn -from the 'vacuum tower through coolers 4I, 42

and 43, the separated fractions being run into run-down tanks 46, and 46 respectively. Manifold 41- connects the tanks to the source ofv the vacuum. Pitch-like residue from the ilash distillation is withdrawn from the vacuum tower 40 through bottom line 48.

If it is desired further to purify one or several of the alkyl phenol fractions in tanks 44 to 46, a fraction may be conveyed through manifold 49 by pump 50 in line 5I and through heater 52, in which it is heated to about 140-150 C. The heated alkyl phenols then enter oxidizing tower 53 in which they are contacted with air for the necessary length of time, air being introduced through line 54 and unreacted gas being vented through line 55. From the oxidizer 53 the phenols are transferred through heater 56 to distillation column 51, which is preferably kept under substantial vacuum. Alkyl phenols are vaporized and go through condenser 58 in line 59 to tank 60. Line 6I connects tank 58 to the source of the vacuum. If the condensate accumulated in the tank 60 has a foul odor, air may be blown therethrough by way of line 62, whereby the odor is improved.

The aqueous layer in settler 31 comprising largely a sodium carbonate solution usually containing alkali metal naphthenates, a small amount of phenolates and possibly other salts,

is transferred through line 63 to treater 64 wherev an amount of lime is added by way of line 65, sufficient to precipitate substantially all of the carbonates, naphthenates, and other salts. Lime sludge is settled and removed through discharge 86, while recovered alkali metal hydroxide solution is conveyed by pump 6l in line 68 to still 69,

where it is reconcentrated to the required concentration of 35-50%. lfteconcentrated4 alkali metal hydroxide is then returned through lines it, ll and 5 to pump 6 and mixer l as hereinbefore described.

Naphthenic acids may be recovered from the lime sludge by suitable separation of the naphthenates from the carbonates, followed by acidiiication of the former.

The following example further illustrates our process:

A cracked distillate boiling from 180-230 C. obtained in the liquid phase cracking of a Calliornia gas oil was extracted with the proper amount of 40 B. aqueous sodium hydroxide solution, so that about 95% of the free hydroxide was converted to sodium salts of the acidic compounds contained in the distillate. The resulting solution which was turbid and in thin layers of opaque deep red color was steamed for 14 hours and was then allowed to settle. A black sludge settled out which was. removed. Upon further steaming no additional sludge formed. 'I'he resulting clear deep red solution was diluted with about 3 times its own volume of water and was again allowed to settle. This time an oil settled to the top which was removed; into the remaining aqueous solution a measured amount of carbon dioxide was introduced, sufllcient to liberate all the alkyl phenols contained in the alkaline solution.

The liberated alkyl phenols were dark in color. They were separated and quickly distilled in a batch still under an absolute pressure of 10 mm. mercury. The nrst 10%- ofthe distillate were discarded. The following 80% were recovered, and a heavy pitch amounting to about 10% of the charge was left in the still as still bottoms.

The recovered middle fraction was yellowish, and on prolonged standing turned yellowish red.

A portion of this fraction was blown with air at 145 C. yfor about 10 hours, the blown portion was redistilled, and the distillate was again blown for a short time at room temperature. A light yellowish product was obtained which remained pale upon storage for several months. The fol: lowing table shows comparative properties of free alkyl phenols obtained at the various stages of the process:

The alkyl phenols obtained before the oxidation step are suitable as frothing agents in the notation of ores, while the product obtained after oxidation and redistillation meets the requirements for the manufacture of formaldehyde phenol resins.

When it was attempted to purify the alkyl phenols by oxidation without suiiicient steaming, products were obtained which had very poor color stabilities. Furthermore, if the steaming was very far from beingcomplete the products con' tained relatively high amounts of neutral oils and particularly nitrogen bases. The presence of the latter in noticeable proportions precludes the use of the alkyl phenols for most industrial purposes.

In order further to demonstrate the importance of prolonged steaming until substantially al1 sludge forming compounds have been precipitated, comparative runs were made with and without suilcient steaming. Alkyl phenols were extracted from a cracked light stove oil with a 40 Baum sodium hydroxide solution. The

phenolate solution was divided into two portions,

one of which was steamed to completed sludge, precipitation and the other was steamed for a relatively short period`nly, Suillcient, however, to drive off the neutral oils. Both portions were then carbonized to liberate alkyl phenols, which were vacuum distilled to produce three fractions each: a 10% head fraction comprising mainly water, an 80% middle fraction consisting essentially of alkyl phenols, and a 10% residue. 'Ihe nitrogen distribution in these fractions was as follows:

With Without Fraction sumcient sumoient steaming s l Percent Percent Bead fraction 01 06 Middle fraction i. 13 .73 Residue 2. (l) 1. 43

Total 2.14 2.22

As will be noted the prolonged steaming effected a condensation of nitrogen compounds which cannot be vaporized and expelled by steaming and which apparently cannot be re moved in any manner other than by prolonged steaming for a time suiiicient to condense them to tarry condensation products.

We claim as our invention:

1. In the process of producing commercially pure alkyl phenols from a petroleum distillate containing small quantities of the same, the steps comprising extracting the distillate with a quantity of an aqueous alkali metal hydroxide solution of {S-50% concentration to form an alkali metal alkyl vphenolate solution containing free alkali metal hydroxide and a sufficient amount of chemically combined alkyl phenols to prevent precipitation of the alkyl phenolates, said solution containing impurities which form a precipitate only after steaming beyond the point at which the overhead product produced by steaming condenses into a` substantially clear condensate, steaming the resulting `aqueous alkaline solution at about 100 C. to expel volatile impurities whereby an overhead product is' obtained the condensate of which is turbid, until a point is reached in the steaming operation at which said condensate is substantially clear and no longer turbid, continuing the steaming beyond said point at about 100 C. for a time sufficient to precipitate substantially all of the sludges capable of precipitation by steaming, separating the sludges from the solution of alkyl phenolates, carbonating the desludged solution with an amount of carbon dioxide suflicient to liberate alkyl phenols, thereby forming two layers, an alkyl phenol layer and an aqueous layer, separating the layers, and distilling the alkyl phenols under conditions to prevent substantial cracking.

2. The process of claim 1 in which the steaming yis carried out with saturated steam at about containing small quantities oi the same and nitrogen bases commonly associated with petroleum distillates, the steps comprising extracting the distillate with a quantity of an aqueous alkali metal hydroxide solution of 3550% concentration to form an alkali metal alkyl phenolate solution containing free alkali metal hydroxide and a suilicient amount of chemically combined alkyl phenols to prevent precipitation of the alkyl phenolates, and nitrogen bases and other impurities. said solution containing potential sludge which forms a precipitate only after steaming beyond the point at which the overhead product produced by steaming condenses into ,a substantially clear condensate, steaming the resultant aqueous alkaline solution at about 100 C. to expel volatile impurities, thereby precipitating actual sludge and producing an overhead product the condensate of which is turbid, until a point is reached in the steaming operation at which said condensate is substantially clear and no longer turbid, continuing said steaming of the solution at about 100 C. beyond said point chemically to condense nitrogen bases to higher boiling compounds and to precipitate potential sludge until no additional' sludge is precipitated upon further steaming, separating the sludge from the solution of alkyl phenolates, carbonating the desludged solution with an amount of carbon dioxide sufilcient to liberate alkylI phenols, thereby forming two layers, an alkyl phenol layer containing the condensed nitrogen bases and an aqueous layer, separating the layers and distilling the alkyl phenols under conditions to prevent substantial cracking and to retain the condensed nitrogen bases in the residue.

4. In the process of producing commercially pure alkyl phenols from a petroleum distillate containing small quantities of the same, the steps comprising extracting the distillate with a quantity of an aqueous alkali metal hydroxide solution of 35-50% concentration to form an alkali metal alkyl phenolate solution containing free alkali metal hydroxide and a suiiiclent amount of chemically combined allnvl phenols to prevent precipitation oi' the alkyl phenolates, said solution containing impurities which form a precipitate only after steaming beyond the point at which the overhead product produced by steaming condenses into a substantially clear condensate, steaming the resulting aqueous alkaline so- 'lution at about 100 C. to expel volatile impurities, whereby an overhead product is obtained the condensate of which is turbid, until a point is reached in the steaming operation at which said condensate is substantially clear and no longer turbid, continuing the steaming beyond said point at about 100 C. for a timesuicent to precipitate substantially all of the sludges capable of precipitation by steaming, separating the sludges from the solution of alkyl phenolates containing emulsied organic matter, diluting the desludged solution with at least an equal volume of water, thereby precipitating the emulsiiied organic matter,l separating the precipitated matter from the solution of phenolates, carbonating the diluted solution with an amount of carbon dioxide suiiicient to liberate alkyl phenols, thereby forming two layers, an alkyl phenol layer and an aqueous layer, separating the layers and distilling alkyl phenols under conditions to prevent substantial cracking.

5. In the process of producing commerciallyl pure alkyl phenols from a petroleum distillate containing small quantities of the same, the steps comprisingy extracting the distillate with a quantity of an aqueous alkali hydroxide solution of 3550% concentration to form an alkali metal alkyl phenolate solution containing free alkali metal hydroxide and a suicient amount o! chemically combined alkyl phenols to prevent precipitation of the alkyl phenolates, said solution containing impurities which form a precipitate only after steaming beyond the point at which the overhead product produced by steaming condenses into a substantially clear condensate, steaming the resulting aqueous alkaline solution at about 100 C. for a time sumcient to expel volatile impurities, and beyond the point at which an overhead product is produced which condenses into a substantially clear condensate, thereby to precipitate substantially all the sludges Acapable of precipitation by steaming, separating the sludges from the solution of alkyl phenolates, carbonating the desludged solution with an amount of carbon dioxide suiiicient to liberate .alkyl phenols, thereby forming two layers, an

7. In the process of producing commercially pure alkyl phenols from a petroleum distillate containing small quantities of the same, the

steps'comprising extracting the distillate with a quantity of an aqueous alkali metal hydroxide solution of 35-50% concentration to form an alkali metal alkyl phenolate solution containing free alkali metal hydroxide and a sufficient amount of chemically combined `alkyl phenols to prevent precipitationof the alkyl phenolates. said solution containing impurities which form a precipitate .only after steaming beyond the point at which the overhead product produced by steaming condenses'into a substantially clear condensate, steaming the resulting aqueous alkali solution at about 100 C. for 4 to 16 hours, beyond the point at which an overhead product is produced which condenses into a substantially clear condensate thereby precipitating actual and potential sludges, separating the sludges from the solution of alkyl phenolates, carbonating the desludged solution with an amount of carbon dioxide suiicient to liberate alkyl phenols, thereby forming two layers, an alkyl phenol layer and an aqueous layer, separating the layers, and distilling the alkyl phenols under conditions to prevent substantial cracking.

8. In the process of producing commercially pure alkyl phenols from a petroleum distillate containing small quantities of the same, the

steps comprising extracting the distillate with point at which the overhead product produced by steaming condenses into a substantially clear condensate, steaming the resulting aqueous alkathereby to precipitate actual and potential sludges, separating the sludges from the solution of alkyl phenolates containing emulsifled organic matter, diluting the desludged solution with an amount of water suilicient to produce a diluted solution containing about 10% alkyl phenolates.. vthereby precipitating the emulsied matter, separating the precipitate from the solution, lcarbonating the diluted solution with an amount of carbon 'dioxide sumcient to liberate` alkyl vphenols, thereby forming two layers, an alkyl phenol layer and an aqueous layer, separating lthe layers and distilling alkyl phenols under conditions to prevent substantial cracking.

WALTER J. HUND. SAMUEL BENSON THOMAS. DANIEL B. LUTEN, JR. 

